Reaction of olefins with cf2clcfcl2



Q.,.UN; J ED. ATE REACTION or OILEFIINS WITH F. Beasley and William'A. st ws,W601i .3

. bury,-N. .L, assignors to Sticony-VacumiOil Incorporated, a corporation of New l Charles Company, "York.j

' No sawing. Application Ms Serial No. 747,320

This invention relates to a methodflof reactin olefins with alkyl halides in the presence of an oxygen-containing gas, and to the products of such reaction. I

M. S. Kharasch, Elwood V. Jensen, and W. H.

Urry have reported the addition of carbon tetrachloride and chloroform to olefins using diacyl peroxides (Science, "102, 120119451). Likewise, they have studied the addition of chlorinated acid derivatives such as CI-lzClCOzCI-Iiand'CClaCOCl (J. Am. Chem. Soc. 67,1626 [-1945]; the addition or P013 (J. Am. ChemI'Soc 67,1864 [1945]). and

CBI4 or CHBrs to'1-olefihs using very small pro- UnitedStates Letters Patent 2,068,772 deals with the addition of CH3CHC12 to vinylchloride or 1,2-dichloroethylene using aluminum chloride at a temperature of 20 C. Chloroform has been added to tetrachloroethylene in .the presence of aluminum chloride to obtain heptachloropropene I (J. Prakt. Chem. 89, 415) The addition of halides to olefins in thepre's ence of hydrogen fluoride has been described'in United States Letters Patent application, Serial No. 549,762, filed by Badertscher and Feasley on August 16, 1944, now abandoned.

There are many patents dealing with the addition of hydrogen halides to olefinic materials to give halides or polyhalides.

temperature of 300 C. using a silver reactor.

United States Letters Patent 2,365,516 deals with: the same addition using activated carbon. Hy- 7,

United States Lets ters Patent 2,393,304 deals withthe addition of hydrogen chloride to tetrafiuoroethylene 'at'a r o crolz' I 9a 1947,. i i

. 2% drog'en bromide has been added to olefins using peroxides to get addition contrary to Marko w nikovs rule (United (States Letters Patent 2,058,465) United States Letters Patent 2,058,466

deals with the normal addition of hydrogen halides in the presence of thiophenol' or thiocresol.

Hydrogen halides have been added to" olefinic materials using various acidic catalysts or Friedel-Crafts catalysts (United States Letters-Patent 2 ,016,072 employs sulfuricacid; Unite'd'States Letters Patent2',0131,228 employs alkylhalosulphonates; United States'Lette'rs' Patent 2,094,064 makes use of silica 'gel, zinc chloride drstan'nic chloride; United States Letters Patent-2,125,284 employs ethyl sulfuricacid' with bismuth chloride; United States 'LettersPatent 2,123,504 deals with the addition of H01 to-butadiene using copper halides; United States Letters" Patent 2,140,927, 2,179,218, and 2,209,000 eniployaluminuni chloride of ferric :chloridey iUnit'ed States Letters Patent 2,144,816 m'akes use of .kieselguhr or acids'of phosphorus at temperatures of 200- 500 F; and United States Letters Patent 2,174,278 employs bismuth chloride at tempera- V tures of 100-250 C.) to form halides.

Halides have likewise been prepared from alcohols using hydrogen halides (United States Letters Patent 2,090,722 deals with the preparation of fluorides from alcohols and hydrogen fluoride), halides of phosphorus (see United States Letters Patent 2,099,357) or similar reagents such as thionyl chloride, etc.

' No reference was found to the use of air to bring about the addition of any alkyl halides to 'olefins. According to the present invention is has been found that any alkyl halide may be readily reacted with any olefinic material, in the presence *of airor oxygen, to give a halide of higher molecular weight. The resultant products are particularly useful as refrigerants, insecticide ingreclients, selective solvents for petroleum refining,

transfer agents and the like.

i The process of preparing these new reaction stable synthetic lubricants, hydraulic fluids, heat even more carbon atoms per molecule.

, 3 V 7 products is superior to processes which add polyhalides such as carbon tetrachloride to olefins', by

the use of peroxides, acids or Friedel-Crafts catalysts, because it can be accomplished simply and easily without the use of an expensive catalyst which isdifficult, if not'impossible, to remove from the products and recover for reuse. Furthermore, the reaction products of this invention are diiierent from those produced by the above mentioned processes.

VREACTANTS The preferred olefins for the reaction of this invention are simple, straight-chain primary olefins containing from,2 to 20 carbon atoms.- However, branched-chain olefins, olefins containing a plurality of double bonds per molecule, c'yclo-olefins, such as cyclohexene, and olefins containing various substituentsmay bealso utilized. still further, halides, alcohols'and the likeLwhich are readily converted into olefins may be usedin place of olefins. The olefinused may be a single, pure olefin, a mixture of pure jolefins, a commercial olefin, or a commercial mixture of olefins.

oxides should be used in a gaseous phase. The reaction using the free oxygen-containing gas of this invention, is quite different from the reaction accomplished in the presence of peroxide, hydrogen chloride, or the like, and produces a different type of product.

REACTION CONDITIONS found preferable to use as much pressure as can be safely used without danger of explosion. High pressures appear to definitely favor the reaction,

but the reaction proceeds even at pressures as The halides used preferably contain between .1 and 24 carbon atoms, inclusive, but may contain examples, which follow, polyhalides were used, but'it is to be understood that monohalides can be used, halides containing only ;one kind of halogen can be used, or halides containing twoor more 'difierent kinds of halogens can be used. Furthermorepthe alkyl halides may be either saturated 'orunsaturated and may contain aryl,

hetero, cycloalkyl, alkaryl, aralkyl, heteryl (such as thien-yl', pyrryl, etc.), alkheteryl (such as methyl thienyl, etc.), hetero-alkyl, cyanide, sulphate, nitrocarboxyl, hydroxyl, or the like substituents. As; with the olefin,'the alkyl halide may be a single, chemically pure alkyl halide, a :mixture of chemically purealkyl halides, a commercial-alkylihalide, or a commercial mixture ,of alkyl halides. V

fThe'oxygen-containing gas used. in the reaction can be described as any gas which contains free -oxygen,:s uch'for example as air and oxygen itself. Synthetic mixtures of oxygen and an inert gasrsuch as helium could be used. The free oxygencontaining gas of this invention is to be idistinguishedirom such materials as diacyl per- -oxids-, and other peroxides, even if these per- In the low as 100 "pounds per square inch. The preferred range 'of pressure is from 600 to 1400 pounds per square inch.

7 The process may be carried out continuously or batchwise'. For example, the reaction may be accomplished in an electrically heated, Monel lined, rocking bomb, into which the reactants and the oxygen-containing gas are charged. The bomb is "then rocked and heated for the desired periodof time, after which it is chilled and the oxygen-containing gas vented, The product is thereafter distilled to remove unreacted polyhalides and olefins and .to separate the various fractions of the product; r

The proportion of air or free oxygen-containing gas used is not highly critical. Proportions have been successfully used ranging from 0.31% by weight-ofoxygen (as-air) to 1.01% by weight of oxygen (asair), based on the total-weight of the reactants, As little as 0.5% oxygen can be used, or as much as oxygen can be used, satisfactorily. If a percentage of oxygen much less than 0.5% is used, the reaction is slowed down,- whereas if appreciably higher percentages than 5.0% are used, the products are unnecessarily'diluted with the free oxygen-containing "By way of example," the following table shows the results of nine reactionsperformed in the manner described:

: Table Reactants Com pound dlIlS.

Catalyst Tell-up.

Contact Time, 'Hrs.

Product {orioiorohn (Freon 113) Pentene-l CFZCIOFOIL--- (Freon 113) I Octene-i CFgOlOFCIp--.

(Freon 113) Cyclohexene. CFzOlOFChn (Freon 113) Octene-2 OChFn (Freon 12) ,r Octene-L.

{Decene-l son- 6 0' PRODUCT Fraction Weight of Sp Percent Percent Run Number Fraction Gr F. 01 Remarks 68. 0.95 0. 1 0. 61 10. 5 1. 01 24. 6 30. 46 24. 5 1.02 21. 4 32. 42 Solid 5. 5 0. 92 6.8 8. 70 72. 0 0. 99 14. 2 24. 71 r 23.0 0. 89 20.8 29. 04 Solid 37. 0 1. 09 17. 5 29. 19 11.0

TotaL. 104. 5 2 6 1 9 4:75 1315 III: 78. 5 0. 79 6. 9 74' 0.88 18. 2 72. 0 0.98 21. 3 1. 00 1 30. 5 60 0.88 10.0

1 0 011120013 has 29.6% chlorine. 2 Chiefly recovered decene-l.

The characteristics of the reaction products 2 indicate that they are mixtures of a number of different chemical compounds. It is within the scope of this invention to use any such mixtures, as produced, or to separate from any such mixture either by fractional distillation, solvent extraction, or otherwise, any fraction thereof, which is found suitable for any particular purpose. The higher boiling fractions will be more suited for use as synthetic lubricants, or addition agents for mineral oil, or as carriers for insecticides, whereas the lower boiling fractions will be more suitable for use as refrigerants, selective solvents, and the like.

We claim:

1. A method for effecting the condensation of a mono-olefin, selected from the group consisting of aliphatic mono-olefins and alicyclic mono-olefins, with a compound of the formula CFzClCFClz, which comprises heating a mixture of said monoolefin and said CF2C1CFC12, in which mixture said CFzClCFClz is present in molecular excess, in the presence of between 0.3% and 5.0% by weight of oxygen, based on the total weight of the reactants, at a temperature of at least 25 C. and. 55

at a pressure of at least 100 pounds per square inch.

2. A method for effecting the condensation of octane-2 with a compound of the formula CFzClCFClz which comprises heating a mixture of said octene-2 and said CF2C1CFC12, in which mixture said CF2C1CFC12 is present in molecular excess, in the presence of from 0.3% to 1% of oxygen based on the total weight of the reactants, at a temperature of from about 100 C. to about 250 C. and at a pressure of from about 600 to about 1400 pounds per square inch.

3. A method for effecting the condensation of cyclohexene with a compound of the formula CF2C1CFC12 which comprises heating a mixture of said cyclohexene and said CF2C1CFC12, in which mixture said CFzClCFClz is present in molecular excess, in the presence of from 0.3% to 1%-of oxygen based on the total weight of the reactants, at a temperature of from about C. to'about 250 C. and at a pressure of from about 600 to about 1400 pounds per square inch.

4. A method for effecting the condensation of octene-l with a compound of the formula CFzClCFClz which comprises heating a mixture of said octane-1 and said CF2C1CFC12, in which mixture said CF2C1CFC12 is present in molecular excess, in the presence of from 0.3% to 1% of oxygen based on the total weight of the reactants, at a temperature of from about 100 C. to about 250 C. and at a pressure of from about 600 to about 1400 pounds per square inch.

CHARLES F. FEASLEY. WILLIAM A. STOVER.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,440,800 Hanford et a1 May 4, 1948 2,468,208 Kharasch Apr. 26, 1949v FOREIGN PATENTS Number Country Date 581,899 Great Britain Oct. 29, 1946 

1. A METHOD FOR EFFECTING THE CONDENSATION OF A MONO-OLEFIN, SELECTED FROM THE GROUP CONSISTING FO ALIPHATIC MONO-OLEFINS AND ALICYCLIC MONO-OLEFINS, WITH A COMPOUND OF THE FORMULA CF2CICFCI2, WHICH COMPRISES HEATING A MIXTURE OF SAID MONOOLEFIN AND SAID CF2CICFCI2, IN WHICH MIXTURE SAID CF2CICFCI2 IS PRESENT IN MOLECULAR EXCESS, IN THE PRESENCE OF BETWEEN 0.3% AND 5.0% BY WEIGHT OF OXYGEN, BASED ON THE TOTAL WEIGHT OF THE REACTIONS, AT A TEMPERATURE OF AT LEAST 25* C. AND AT A PRESSURE OF AT LEAST 100 POUNDS PER SQUARE INCH. 